Azo dyes



Patented June 11, 1940 UNITED STATES PATENT orncs AZO DYE-S Swanie S.Rossander and Ghilcs E. Sparks, Wilmington, Del., assignors to E. I. duPont de Nemours & Company, Wilmington, DeL, a corporation of Delaware NoDrawing. Application March 29, 1939, Serial No. 264,837

18 Claims.

This invention relates to azo dyes, to direct dyes, to dyesafter-treated with formaldehyde, and to metalized dyes.

Direct azo dyes are those which dye the clothdirectly from a water bathwithout subsequent treatment to bring out the color; Many examples ofsuch direct dyes are recorded in the literature of the trade. Thesedirect colors are generally substantive to cotton and other forms ofcellulose and regenerated cellulose, giving bright shades, but havingonly moderate fastness to light. These direct colors show considerableloss in strength and impart an undesirable stain to associated uncoloredor differently colored l5 fibers when they are washed. Direct colorswith generally faster to washing than the corresponding direct colors,but they are duller, more costly, more costly to apply as such dyeingoperations require much labor and the dyeings change shade duringdevelopment.

It is an object of this invention to provide a class of colors havingthe simplicity of applica tion and constant, bright shade of the directcolors, and washing fastness superior to the di rect colors. Anotherobject of the invention is to provide methods of applying the colors,and of increasing their light fastness.

The objects of the invention are accomplished in general by applying tothe material to be dyed, the direct polyazo dyes represented by theformula 0 A X Y- Z -X A and after-treating the dyed fabric withformaldehyde, formaldehyde and a soluble metal salt, or 45 a solublemetal salt.

The symbol A in the foregoing formula is a metadihydroxy benzenerepresented by the formula OOH in which R is one of a group consistingof hydrogen, alkyl, alkoxy, aralkyl, hydroxy, amino, halogen, nitrile,carboxy and sulfonic acid.

The symbols X are diamino-diphenylene compounds in which the aminogroups are in meta or para positions to the bridged carbons and arerepresented by the formula NH? NHz gymag;

(B1) (B1)" in which B is one of a group consisting of --O, -S-, NH-,NHCONH, --NHCSNH--, -CONH, CONH(CH2) mNHCO--, --I-IC= CH--,

wherein the -NHCO groups are meta or para to each other, --O(CH2)mO-,-S(CH2)mS-, --N=N--,

O 35 and -(CH2)m--, n is an integer l or 2, m is 2 to '7, R1 is at leastone of a group consisting of hydrogen, alkyl, alkoxy and halogen andwhere there is more than one R1 the substituents may be alike ordifferent. R2 is one or more than one of said group hydrogen, alkyl,alkoxy and halogen in any combination thereof. In cases Where n is l. inthe group --(B)n1- the symbol X stands for a diamino diphenyl, such asbenzidine, or one of the indicated derivatives thereof.

7 amino, hydroxy and alkylated amino.

The symbol Y is an amino naphthol sullfonic acid represented by theformula OH. NHz

in which amino is in the 1 or 2 position, R3 is one of a groupconsisting of hydrogen, alkyl, alkoxy, aralkyl, nitro, halogen, nitrile,sulfonic acid and carboxy.

The symbol Z is a compound of the benzene series represented by theformula in which R5 is one of a group consisting of hy drogen, alkyl,alkoxy, phenyl-alkyl, hydroxy, amino, alkylated amino, halogen, CN andsulfonic acid, and each R4 is one of a group consisting of The R4 groupsmay be alike or unlike.

In general R, R1. R2, R3 and R5 may be sub stituted in any open positionof the aryl nuclei, except where the formulas indicate that the positions of such substituents are fixed. The term alkylated amino as usedin the specification and claims refers to the secondary or tertiarygroup in which X1 and X2 may be alike or different groups, X1 is alkyl,phenyl-alkyl or hydroxy alkyl and X2 is hydrogen, alkyl, phenyl-alkyl orhydroxy alkyl. As illustrations of alkylated amino groups are mentionedthe groups N(CI-I3)2, NII CH3, NCH3 (C2H4OH) NCH3 (Cal-I5) -N 21((12 H9H) N(C2 H4 0 H) (3 H2 Ct H5, -N1-I-C4I-I9 and N(C4H9)2. Alkyl in thespecification and claims refers to straight and branched chain aliphaticgroups having 1 to 4 carbons, alkoxy refers to the corresponding alkoxygroups and halogen refers to any of the halogens.

The compounds of the invention may be made in general by coupling onemoi equivalent of the diamino compound Z to one mol equivalent of thediazo of the naphthol amino sulfonic acid compound Y, isolating theresulting compound 1+2 and then dissolving it in basic solution. Two moiequivalents of the diamino diphenyl compound X are then tetrazotized andcoupled in basic medium with the one moi equivalent of the compound Y-Z. This produces a basic tetrazo solution of the compound X Y z X. Thiscom pound is then coupled in basic medium with two mol equivalents ofthe dihydroxy phenyl compound A and the product A+X Y Z -X A is isolatedby appropriate means, as by salting out and filtering.

Dyeings may be made in general by dissolving the products A+X+Y Z X A ina suitable solvent such as water. Dyeing assistants and other compoundswhich are necessary or desirable to produce dyeings on fabrics can beadded to the solution to make the dyebath. The material to be dyed isthen immersed in the dyebath which may have been previously heated. Whendyed the material is after-treated in a bath containing formaldehydeuntil a formaldehyde compound or complex is formed. The resultingdyeings have excellent washing fastness. If improved light fastness isdesired, this can be obtained by additionally treating the dyeing in abath containing a soluble metal salt, such as copper sulfate.

The invention will be more fully set forth in the following moredetailed description which includes examples that are given asillustrative embodiments of the invention and not as limitationsthereof.

EXAMPLE 1 Slurry 34.1 parts of the mono sodium salt of 2-amino-8-naphthol-3,6-disulfonic acid with 300 parts of water. Addapproximately 4.0 parts of sodium hydroxide to the slurry and stir untila complete solution is obtained which is faintly alkaline to BrilliantYellow paper. Cool to 0 C. with ice and add 14.5 parts of 100%hydrochloric acid as a 30% solution. Slowly add to this solution 6.9parts of 100% sodium nitrite as a 30% solution. Maintain a slight excessof nitrite in the mixture for 15 minutes whilst it is cooled to 0-5" C.Finally balance to a very faint or negative nitrite test by the additionof a neutral solution of the diazo component.

Dissolve 10.8 parts of 1,3diamino-benzene in 200 parts of water at 50-60C. Cool to 25 C. with ice and add the cooled mixture rapidly to theabove described diazo of 2-amino-8-naphthol- 3,6-disulfonie acid. Stirminutes then add slowly during 30 minutes 11.0 parts of sodium carbonateand finally stir the mixture for two hours. The suspension is producedwhich is neutral to Congo red papers and is neutral to slightly alkalineto Brilliant Yellow paper. There should be an excess ofl,3-diaminc-benzene present and the mixture should give no test fordiazo.

Make the above described suspension acid to Congo red papers by adding73.0 parts of 100% hydrochloric acid as a 30% solution. Salt slowly(25%) with sodium chloride. Stir one hour and filter.

Dissolve the filter cake in 1000 parts of water at HP-50 C. by theaddition of approximately 32.0 parts of sodium carbonate and then coolto 20 C. by adding ice.

Slurry 36.8 parts of 4,4-diaminodiphenyl with 1000 parts of Water. Add37.0 parts of 100% hydrochloric acid as a 30% solution and cool to 0 C.with ice. minutes by adding 27.6 parts of 100% sodium nitrite as a 30%solution. The tetrazo-should be free of insoluble matter and thereshould be an excess nitrite.

Make the above described tetrazo distinctly alkaline to Brilliant Yellowby adding 64 parts of 100% sodium carbonate as a 5% solution. Whilemaintaining a temperature of 0-5 add the alkaline solution of2-amino-8-naphthol3,6-disulfonic acid- 1,3-diamino-benzene slowly to thecold alkaline tetrazo until there is no test for 4,4- diamino-diphenyltetrazo. It is desirable to remove a portion of the tetrazo, say 5 tobefore the latter addition is made so that the portion can be used tobalance the coupling.

Immediately upon the disappearance of the l,i-diamino=diphenyl tetrazo,add rapidly 33 parts of 1,3-dihydroxy-benzene and stir the mixture forone hour. Keep the suspension alkaline to Brilliant Yellow and maintainan excess of 1,3- dihydroxy-benzene.

After stirring, the suspension was heated to 70-80 C., salted slowly(10%) with sodium chloride, filtered and dried in an oven at 80-85 C.The dry powder was deep brown in appearance.

Tetrazotize at 0-5 C. for30-40 The compound is represented by theformula A fabric of regenerated cellulose rayon was dyed with the dyeand after-treated as follows.

A solution of the dye was made by dissolving 0.2 gram of the dye in 50cc. of water at 190-200 F. and adding .04 gram of sodium carbonate toassist the solution. The bath was diluted with hot water at 160 F. to atotal volume of 500 cc. whilst stirring and 40 cc. of a 10% solution ofGlaubers salt were added. A 10 gram piece of regenerated cellulose rayonwas wet out with water, squeezed partially dry and entered into thedyebath. The temperature of the dyebath was raised to 180-190 F. duringa period of fifteen minutes and was held at that temperature for onehour. The dyeings were stirred at frequent intervals. At the end of onehour the dyeing was removed and rinsed in cold water.

Ajter-treat2nent in a fresh bath The rinsed dyeing from the aboveoperation was entered into 500 cc. of water at 130-140 F.

and approximately 10 cc. of 10% formaldehyde (25 cc. of approximately37% formaldehyde by weight diluted to 250 cc. with water) were added.The bath was held at this temperature for twenty minutes. The dyeing wasthen removed, rinsed and dried.

"After-treatment in the dye bath Slurry 42.5 parts of4,4-diamino-azobenzenes with 1000 parts of water. Add 37 parts of 100%hydrochloric acid as a 30% solution. Ice to 0 C. Tetrazotize at 05 C.for 30-40 minutes with 27.6 parts of 100% sodium nitrite as a 30%solution. The tetrazo should be free of insoluble matter and thereshould be present an excess of nitrite. Balance to a very faint excessof nitrite.

Add approximately 100 parts crystalline sodium acetate to the tetrazo.The tetrazo solution should be neutral to Congo red paper. To theneutralized tetrazo, a slightly alkaline solution of the mono-azoproduct, 2-amino-8-naphthol-3,6- disulfonic acid- 1,3-diamine-benzene,prepared as in Example 1, is added until there is no test for4,4'-diamino-azo-benzene tetrazo.

Immediately upon the disappearance of the 4,4-diamino-azo-benzenetetrazo, add rapidly 33 parts of 1,3-dihydroxy-benzene. Add slowlyapproximately 60 parts of sodium carbonate to make the suspensionalkaline to Brilliant Yellow. There should be an excess of1,3dihydroxy-benzene.

Heat the suspension to '70-80 C. Salt slowly 10% with sodium chloride.Filter. Dry at C. in an oven. The dry powder was a deep brown inappearance.

The dye is represented by the formula OH I|-IH2 l[l-- -N=NC -NH2 NsOaSS0sNB if? N Regenerated cellulose rayon was dyed with the dye andafter-treated as described in Example 1. A dyeing with a deep brownshade was obtained which showed good fastness to washing. The dyeing hadbetter fastness to washing than the direct dyeing.

EXAMPLE 3 A product represented by the following formula was obtained bysubstituting 48.5 parts of di(3- aminophenyl) urea for 36.8 parts of4,4'-diaminodiphenyl in Example 1.

Regenerated cellulose rayon was dyed with the dye and after-treated asin Example 1. A dyeing with a yellow brown shade was obtained whichshowed good fastness to washing. The washing fastness was better thanthe direct dyeing.

It is to be understood that modifications in the methods of preparingthe compounds can be made and the invention is not limited by thedetails particularized in the examples. The compounds can be prepared bysuitable modifications of the methods set forth without departing fromthe invention as will be understood by those skilled in the art.

The following are additional illustrations of the invention. Theseproducts were prepared by methods similar to those recited in theforegoing examples. The most applicable variations in the method ofmaking these compounds is apparent to those skilled in the art for anygiven example, wherever a variation is desirable. The direct dyeings witthe colors on regenerated cellulose rayon and after-treatn1ent withformaldehyde gave bright shades which were comparable in brightness andWashing fastness to those pro- As other illustrations of meta-dihydroxyherizenes which may be used as the component A are mentioned:

3,5-dihydroxy toluene,

3,5-dihydroxy anisole,

3,5-dihydroxy benzoic acid, 1,3-dihydroxy benzene-S-sulfonic acid,1,3-dihydroxy-5 amino benzene, 1,3-dihydroxy-5-chloro-benzene,1,3-dihydroxy-S-bromo-benzene, 1,3,5-trihydroxy benzene,1,3-dihydroxy-5-benzo-nitri1e and l-benzyl-3,5-dihydroxy benzene.

As other illustrations of Y compounds the fol= lowing naphthalenederivatives are mentioned:

2-amino-3-methyl-5-hydroxy-7 -sulfonic acid,

2-amino-3-methoxy5-hydroxy-7-su1fonic acid,2amino-3-benzyl-5-hydroxy-7-sulfonic acid,2-amino-3-nitro-5-hydroxy-7-sulfonic acid,2-amino-3-ch1oro-5-hydroxy-'7-sulfonic acid,2-amino-3-bromo-5-hyd1'oxy-7-sulfonic acid, 2amino-3-nitrile-5-hydroxy-7-sulfonic acid,2-amino-3-carboxy-5-hydroxy-7-su1fonic acid,

duced 1n t e f r e a p 1- and 2-amino-8-naphtholfi-sulfomc acids,

Example Constitution Shade 4 1,3-dihydroxybenzene 4,i-dia1nino-dipheny12-an1ino-8-naphtl1ol-3,6-disulfonic acid 1,3-dihydroxy- Brown benzenee4,4-diamino-d1phenyl l,3-dihydroxy-benzene.

5 l 3,5-dihydrXy-toluene 4,4-diamlno-diphenyl2-aminc-8-naphthol-3,6-disu1fonic acid 1,3-diamino- Do.

benzene 4,4-diamin0-d1phenyl 3,5-dihydrcxy-toluene.

6 .7 1,3-dihydroxy enzene e 4 ,4-diamin dipheny1lamino-8naphthol'3,6-disulfonic acid 1,3-diamino- Do benzene e-4,4diamino-oiphenyl dihydroXY-benzene.

7 1,3-dihydroxybenzene e- 4,4-diamino-dipl1enylz-aniino--naphthol-7-sulfcnic acid 1,3-diamino-benzene 0-4,4-diamino-diphenyl 1,3-dihydroxy-benzenc.

3 1,3-dihydroxybenzene 4,4-diamino-diphenyll-amino-5-naphthol-7-su1ionic acid 1,3dia1nino-benzene -Do.

4,4"diamino-diphenyl 1,3-dihydroxy-benzene.

9 1,3-dil1ydroxybenzene -4,4-dian1ino-diphenyl2-amino-8-naphthol-6-sulfonie acid 1,3-diamino-benzene D0-4,4-diamino-diphenyl 1,3-dihydroxy-bcnzene.

10 1,3-dihydro y enzene 4,4-diaininostilbene2-amin0-S-naphthol-3,6-(lisnlfonic acid 1,3-diamino-ben- Do.

zene 4,4-diamino-stilbene 1,3-dihydroXy-benzene.

11 1,3-dihydroxybenzene 3,3-diamino-azoxy-benzene2-amino-8-naphthol-3,6-disulfonic acid 1,3-diamino- Yellow rown.

benzene 3,3-diamino-azoxy benzene 1,3-dihydroxybenzene.

12 1,3-dihydroxybenzene e- 4,4-dian1ino-dipheny12-amino-8-naphthol-3,6-disulfonic acid 9 5-methoxy-1,3- rodihydroxy-benzene 4,4-diamino-diphenyl 1,3-dihydroxy-benzene.

13 1,3-dihydroxybenzene 4,4-diamino-diphenylZ-amino-8-naphthol3,6-disulfonic acid l,3-diamino-4 0- methyl-benzene4,4-diamino-dipl1enyl 1,3-dihydroxybenzene.

y y ne 3,3-diamino-azoxy-benzcne 2-amino-8-naphthol-3,6-disulionic acid1,3-di- D0- hydroxy-benzenc 8,3-diaminoawn-benzene 1,3-dihydroxybenzenc.

15, 1,3-dihydroxybenzene (MY-diemino-diphenyl-amine-2-sulfonic acid)2-amino-S-naphthol-3,fi-disulfonic Do.

acid 1,3-diamin0-benzene (4,4-diamino-diphenyl-amine-2-sulfonie acid)1,3-dihydroxy-benzene l6 ...l. l,3-dihydroxybenzene 2,2dichloro-4,4-dian1ino-dipl1enyl 2-an'1ino-8-naphthol-3,B-disulfonio acid1,3- D0.

diamino-benzene 2,2-dichloro-4,4-dicmino-diphenyl 1,3-dihylroxy-benzcne.

170"... 1,3-dil1ydroxybenzene (3-(4-aIninobenz0yl-amn1o)-1-aminobenzene)2-amino-8-naphthol-3,6-disulfonic Do. acid 1,3-diamino-benzene(3-(4-amino-benzoyl-an1ino)-1-an1ino-benzene) 1,3-dihydroxy-benzene.

18 1,3-dihydrnxybenzene (1,3-di(4-amino-benzoylamino) benzene)2-amino-8-naphthol-3,6-disulfonic ellow brownacid 1,3diamino-benzene(l,3-di(4-ainino-benzoyl-amino-benzene) 1,3-dihydroxy-benzene.

19 1,3-dihydroxybenzene l,2-di(4-aniino-benzoyl amino) ethaneZ-amino-8-napl1tl1ol-3,6-disulfonic acid- D04 1,3-diamino-benzenel,2-di(4-an1ino benzoylamino) ethane 1,3-dihyd1'oxy-benzene.

20 .l 1,3-dil1ydroxybenzene di( i-amino-2-methyl-phenyl) ureaZ-ainino-8-naphthol-3,G-disulfonic acid 1,3- Brown.

diaminobenzene di(4-an.1ino-2-methy1 phenyl) urea1,3-dil1ydroxy-benzene.

21 1,3-dihydroxybenzene(4-(4-amino-benzoyll-alnino)-5-Incthoxy-2-n1ethyl-l-amino-benzene)2-amino-8- 0.

naphthol-3,6-disulfonic acid 1,3-diamino-benzcne e(4-(4-amino-benzoyl-amino)-5-meth0xy-2-methyl- Lamina-benzene)1,3-dihydroxy-benzene.

22 1,3-dil1ydroxybenzene e- 4,4-diamino-2,2-din1ethyLdiphenyl-methane2-amino-8-naphthol-3,fi-disulionic Yellow b flwn.

acid 1,3-diamino-benzene 4,4-diamino-2, 2-diniethyl-diphenyl-methane1,3-dihydIoxy-benzene.

23 1,3-dihydroxybenzene 4,4-diamino-diplienyl-sulfide2-amin0-8-naphthol-3,6-disulfonic acid 1,3- r wn.

diamino-benzene 4,4-dian1ino-djphenyl-sulfide 1,3-dihydroxybenzenc.

24 1,3-dihydroxybenzene (-4,4 diamino-diphenylaminc2-arnino-8-naphthol-3,G-disulfonic acid-9 1,3-diamino- D0.

benzene 4,4-diamino-diphenylamine 1,3-dihyclr0xybenzcnc.

25 1,3-dihydroxybenzene ((1,4-d1'amino benzene)(2metl1cxy-5-meLhyl-1amino-benzene 2-amino-8- D0.

naphtho1-3,6-disulfonic acid 1,3-diamino-benzcne ((l,4-dia1nino-bcnzene)(Z-methoxy-fi-methyl-lamino benzene 1,3-dihydroxybenzene.

1,3-dihydroxy-benzene 4,4-diamino-diphenyl2-amin0-8-naphthol-3,6-disulfonic-acid1,3-diaminobcnzene-4-sulfonic-acid 4,4-diamino-diphenyl1,3-dihydroxy-benzene.

27 1,3dihydr0xy-benzene 4,4-diamino-diphenylZ-amino-S-naphthol-3,6-disu1fonic acid 1,3-diamin0-4- D0.

chloro-benzene 4,4-diamino-diphenyl 1,3-dihydroxy-bcnzene.

2S 1,8-dihydroxy-benzene di(4-aI11ino-2-methyl-phenyl)ureaZ-amino-S-naphthol-3,6-disulfonic-acid 1,3- Do.

diamino-benzene di(4amino2-Inethyl-phenyl)urea 1,3-dihydroXy-benzene.

29 1,3-dihydroxy-benzene l,2-di(4-amino-phenoxy) ethane2-an1ino-8-naphthol-3,G-(li-sulfonic-acid 1,3- Do.

diamino-benzene e 1,2-di(4-a1nino-phenoxy)ethane l,3-dil1ydroxy-benzene.

30 U 1,3-dihydroxy-benzeue 4,4-diamino-diphenylether2-amino-8-naphthol-3,6-disulfonie-acid a 1,3-di- D0.

amino-benzene 4,4-diamino-diphcnyl-etlier 1,3-dihydroxy-bcnzene.

31 l,3-dihydroxy-5-Inethyl-benzene 4,4-diamino-(lipheny123mino-8-naphthol-3,fi-disulfonic-acid 1,3- o.

diamino-benzene 4,4-diamino-diplienyl 1,S-dihydroxy-5-u1ethyl-bcnzene.

32 1,3-dihydroxy-benzene 4,4-diamino-diphenyl 2-amino-8-naphthol3,fi-disulfonic acid 1,3-diamino-4- Do.

. benzene-sulfonic acid 4,4-diamino-diplienyl 1,3-dihydroxy-benzene.

33ml..." 1,3-dihydroxy-benzene 4,4-dian1ino diphenyl2-amino-8-naphthol-3,G-disnlfonic-acid 1,3-diamino-4- D0.

chloro-benzene 4,4-diamino-diphenyl l,3-dihydroxy-benzene.

34 1,3-dihydroXy-benzene 4,4-diamino-diphenyl-oxide aZ-amino-8-naphthol-3,6-disulfonic-acid 1,3- Do.

diamino-benzene 4,4-dian1inodiphenyl-oxide 1,3-dihydroxy-benzene.

35 l. 1,3-dihydroxy-benzene 1,2- li(4-amino-phcnoxy) ethane2-amino-8-naphthol-3,6-disulionic-acid 1,8- Do.

diamino-benzene 1,2di(4-aminc-phenoxy) ethane 1,3-dihydroXy-benzene.

As other illustrations of Z compounds are mentioned:

1,3-dihydro-Xy-5-benzo-nitrile, 1,3,5-trihydroxy benzene, 1,2,4-triaminobenzene, 1-dimethylamino-2,4-diamino benzene,l-methylamino-3,5-diamino-benzene, ,3,5-di(ethyl amino) phenol,l-(methyl amino) -3-amino benzene, 1,3-di(ethyl amino) benzene,l-hydroXy-3-amino benzene, l,3-di(ethyl amino) benzene,1,3-dihydroxy-benzene-5-sulfonic acid, 1,3-dihydroxy-fi-methyl-benzeneand ZA-diamino benzoic acid.

As other illustrations of X compounds are mentioned:

4,4-diamino-3,3'-dimethyl-diphenyl, 2,2 dichloro 4,4 diamino -3,3-dimethyl-diphenyl, 4,4-diamino-3,3'-dimethyl-diphenyl-oxide,4,4-diamino-3,3-dimethyl-diphenyl-sulfide, 4,4 diamino-2,2dimethyl-diphenylamine, di (2-methyl-5-amino-phenyl) urea, di(4-amino-2methoxy-phenyl) urea, di(4-aminophenyl) thio-urea, 4-(4-amino-benzoyl-amino) 3-methyl=1-amino-= benzene,1,3-di(4-amino-benzoyl-amino) propane, l,3-di(4'-amino-benzoyl-amino) 4w methyL-ben zene, 1,2-di(4'-amino-2methoxyphenoxy) ethane,1,2-di(4-amino-2-methyl-phenoxy) ethane,1,2-di(4-amino-2'-chloro-phenoxy) ethane, 1,2-di (3-amino-phenoxy)ethane, 1,3-di (4'amino-phenoxy) propane, l.,3-di(4' -amino-phenoxy)heptane, l,2di(l-aminophenyl-thio) ethane, 1,3-di (4'-amino-phenyl-thio)propane, 4,4'-diamino-azoxy-benzene, 4,4-diamino-diphenyl-ethane. 1,6-di(4'-amino-benzoyl-amino) hexane and 1,6-di (4' -amino-benzoyl-amino)heptane.

Deeper shades and improvement in the light fastness of the dyeings areproduced by after treatment of these colors with water soluble metalsalts such as copper sulfate. For example the after-coppering operationmay be carried out similarly to either of the procedures outlined inExample l'for the after-treatment with formalde hyde, by using asolution containing a 5% solution of hydrated cupric sulfate equivalentin amount to the formaldehyde.

The after-treatment with metal salts may be allowed to continue fortwenty minutes or for such other time as is necessary to metallizethedyeing, at the end of which time the treated dyeings are removed,rinsed and dried. The aftercooperating may replace the formaldehydetreattime to form the formaldehyde compound, the

suitable.

metal salt may be added and the treatment continued for another intervalof time. The dyeings are then removed, rinsed and dried. Similar resultsare obtained by reversing the order of adding the after-treatingreagents, that is by adding the solution of metal salt first, treatingfor the necessary time and then adding the formaldehyde solution. Afterabout twenty minutes the dyeings are removed, rinsed and dried.

The described method of dyeing is typical but it is to be understoodthat the invention is not' limited to the precise concentrations,temperatures and times of treatment specified since these details can bevariously modified as will be understood by those skilled in the art.For example, the after-treatments with formaldehyde or metal-salts maybe carried on for longer or shorter periods and at higher or lowertemperatures than those specified in the illustrations. Any treatmentwhich will form a formaldehyde complex with the dyeing or a metalcomplex with the dyeing, as the case may he, produces the improvedresults. The exact composition of the described formaldehyde and metalcomplexes is unknown to us, but from our investigations it is ourpresent belief that formaldehyde and metal complexes are formed.

Water-soluble salts of various metals can be used for metallizing thedyeings, those having atomic weights between 50 and being the most Asexamples of such metals copper, chromium, nickel, cobalt and iron arementioned. Either watensoluble salts of inorganic or organic acids canbe used, such as sulfates, halides, for mates and acetates, for examplecopper sulfate, nickel sulfate, chromium chloride, copper formate,copper acetate and many other water soluble metal salts of inorganicandorganic acids,

The invention provides bright dyeings having washing fastness equal toand in some cases superior to the diazo colors. The dyeings made inaccordance with the invention are commonly produced more convenientlyand more economically than the diazo colors since in aformaldehydetreated direct dyeing only one bath is required, the dyeingoperations are simple and no change of shade is encountered; whereas ina diazo dyeing at least two baths are required, a change of shade isproduced and the dyeing is a complicated procedure. The dyes may be madein the form of the acid salts of any of the alkali metals by using anappropriate base of the desired alkali metal for neutralization.

Water-soluble salts of various metals can be used for metallizing thedyeings, those having atomic weights between 50 and 65 being the mostsuitable. As examples of such metals, copper, chromium, nickel, cobaltand. iron are mentioned. Either water-soluble salts of inorganic ororganic acids can be used, such as sulfates, halides, formates andacetates, for example, copper sulfate, nickel sulfate, chromiumchloride, copper formate, copper acetate and many other water-sol ublemetal salts of inorganic and organic acids.

Since from the foregoing description of the invention it will beapparent to those skilled in the art that various other embodiments ofthe invention may be made without departing from the spirit and scopethereof, it is to be unden stood that the invention is not limited tothe specific illustrations disclosed.

We claim:

1. A compound represented by the formula in which A is the residue aftercoupling of a meta dihydroxy benzene represented by the formula NHOOwherein the NI-ICO groups are meta or para to each other, -O(CH2)mO-,-S(CHz)miS-, N=N--,

and oi-n)m-, n is an integer not greater than 2, m is 2 to 7, R1 and R2are each from the group consisting of hydrogen, alkyl, alkoxy andhalogen; Y isthe residue of an amino nap-hthol sulfonic acid representedby the formula OH NE:

in which amino is in one of the positions 1 and 2- and R13 is one of agroup consisting of hydrogen, alkyl, alkoxy, aralkyl, nitro, halogen,nitrile, sulbridged carbons and are represented by the formula in whichB is one of a group consisting oI -O-, --S-, --NH-', NHCONH-, -NHCSNH-,-CONH--, CONH(CH2) mNHCO-, HC=CH NHCO (B2)" wherein the -NHCO- groupsare meta or para to each other, --O(CH2)mO-, S(CH2)mS-, N=N-,

and (CH2)m-, n is an integer not greater than 2, m is 2 to 7, R1 is fromthe group consisting of hydrogen, alkyl, alkoxy and halogen and R2 isfrom the group consisting of hydrogen, alkyl,

alkoxy and halogen; Y is the residue of an amino naphthol sulfonic acidrepresented by the formula OH NH;

Hols-wan in which amino is in one of the positions 1 and 2 and R3 is oneof a group consisting of hydrogen, alkyl, alkoxy, aralkyl, nitro,halogen, nitrile, sul fonic acid and carbcxy; and Z is the residue of acompound represented by the formula in which R is one of a groupconsisting of hydrogen, alkyl, alkoxy, phenyl-alkyl, hydroxy, amino,alkylated amino, halogen, CN and sulfonic acid, and the Re groups arelike or difierent members of a group consisting of amino, alkylatedamino and hydroxy.

3. A compound represented by the formula ionic acid and carboxy; and Zis the residue of a compound represented by the formula in which R5 isone of a group consisting of hydro= gen, alkyl, alkoxy, phenyl-alkoxy,hydroxy, amino, alkylated amino, halogen. CN and sulfonic acid and theR4 groups are like or diiierent members of a group consisting of amino,alkylated amino and hydroxy.

2. A compound represented by the formula OH OH in which X is the residueafter tetrazotization of a diphenylene diamine compound in which theamino groups are in meta or para positions to the (B1)" (B1)" in whichR1 is from the group consisting of hydrogen, alkyl, alkoxy and halogen;n is an integer not greater than 2; Y is the residue of an aminonaphthol sulfonic acid represented by the formula OH NH:

"in which amino is in one of the positions 1 and 2 and R3 is one of agroup consisting of hydrogen, alkyl, alkoxy, aralkyl, nitro, halogen,nitrile, sulfonic acid and carboxy; and Z is the residue of a compoundrepresented by the formula in which R is one of a group consisting ofhydrogen, alkyl, phenyl-alkyl, alkoxy, hydroxy, amino, alkylated amino,halogen, CN and sulfonic acid, and the R4 groups are like or differentmembers of a group consisting of amino, alkylated amino and hydroxy.

4. A compound represented by the formula NH, x Q-orr GHQ X Y G in whichX is the residue after tetrazotization of NHOO . wherein the -NHCOgroups are meta or para and '(CH2)111,-, n is an integer not greaterthan 2, m is 2 to 7, R1. is from the group consisting of hydrogen,alkyl, alkoxy and halogen and R2 is from the group consisting ofhydrogen, alkyl, alkoxy and halogen; Y is the residue of an aminonaphthol sulfonic acid represented by the formula OH NH:

in which amino is in one of the positions 1 and 2 and R3 is one of agroup consisting of hydrogen, alkyl, alkoxy, aralkyl, nitro, halogen,nitrile, sulionic acid and carboxy.

5. The compound represented by the formula:

pounds of claim 5.

10. The formaldehyde and metal complexes of the compounds of claim 1.

11-Th6 formaldehyde and metal complexes of the compounds of claim 2. v

12. The formaldehyde and metal complexes of the compounds of claim 3.

13. The formaldehyde and metal complexes of the compounds of claim 5.

14. The process which comprises diazotizing a compound Y which isrepresented by the formula OH NH in which amino is in one of thepositions 1 and2 and R3 is one of a group consisting of hydrogen,

alkyl, alkoxy, aralkyl, nitro, halogen, nitrile, sulfonic acid andcarboxy; coupling with an equimolecular proportion of a compound Z whichis represented by the formula in which R is one of a group consisting ofhydrogen, alkyl, alkoxy, phenyl-alkyl, hydroxy, amino, alkylated amino,halogen, CN and sulfonic acid, and the R4 groups are at least one of agroup consisting of amino, alkylated amino and hydroxy; separating theproduct of coupling Y- z from the coupling medium and making a dilutebasic solution thereof; tetrazotizing about two mol equiva= lents of acompound X which is represented by the formula NH: NH:

I -(B),,1 I (B1) fln in which B is one of a. group consisting of---O---, Y -S, NH-, -NHCONI-I, --NHCSNH-, CONH-, --CONH(CHz)mNHCO-,--HC= CH- NHCO CONH I 5 HIM) wherein the -.-NHCO-- groups are meta orpara l'iH:

sozNfl NH:F

to each other, O(CH2)mO, -s oH2)"ms-,

and -(CH2) 1n, n is an integer not greater than 2, m is 2 to '7, R1 isfrom the group consisting of hydrogen, alkyl, alkoxy and halogen and R2is from the group consisting of hydrogen, alkyl, alkoxy and halogen;coupling said tetrazo with said compound Y Z; tetrazotizing theresulting compound X Y- Z X and coupling with about two mol equivalentsof a meta-dihydroxy benzene which is represented by the formula in whichR is one of a group consisting of hydro gen, alkyl, alkoxy, aralkyl,hydroxy, amino, halo-- gen, nitrile, carboxy and sulfonic acid; and thenseparating the product of coupling from the coupling mixture.

15. The process which comprises dyeing a textile fabric with a compoundrepresented by the formula in which A is the residue after coupling of ameta-dihydroxy benzene represented by the formula OOH

in which R is one of a group consisting of hydrogen, alkyl, alkoxy,aralkyl, hydroxy, amino, halo-- gen, nitrile, carboxy and sulfonic acid;each Xis the residue after tetrazotization of a dipnenylene diaminecompound in which the amino groups are in meta or para positions to thebridged carbons and are represented by the formula and (CH2) m, n is aninteger not greater than 2, m is 2 to 7, R1 is from the group consistingof hydrogen, alkyl, alkoxy and halogen and R2 is from the groupconsisting of hydrogen, alkyl, alkoxy and halogen; Y is the residue ofan amino naphthol sulfonic acid represented by the formula OH NH:

HOaS R:

in which amino is in one of the positions 1 and 2 and R3 is one of agroup consisting of hydrogen,

alkyl, alkoxy, aralkyl, nitro, halogen, nitrile, sulfonic acid andcarboxy; and Z is the residue of a in which R5 is one of a groupconsisting of hydrogen, alkyl, alkoxy, phenyl-alkyl, hydroxy, amino,alkylated amino, halogen, CN and sulfonic acid, and the R4 is at leastone of the group consisting of amino, alkylated amino and hydroxy;suspending the dyed fabric in a hydrous bath containing at leastsufiicient formaldehyde to form a formaldehyde complex with the compoundon the fiber; and heating until said formaldehyde complex is formed.

16. The process in accordance With claim in which the dyed fabric istreated consecutively with first one and then the other of the group ofcompounds consisting of formaldehyde and a soluble metal salt of a metalhaving an atomic Weight between 50 and 65 until a metal and formaldehydecomplex is formed.

17. The compound represented by the formula:

0 H NHi 18. The compound represented by the formula:

NaOaS S O Na SWANIE S. ROSSANDER. CHILES E. SPARKS.

